U.S. patent application number 14/779855 was filed with the patent office on 2016-03-03 for synthetic-resin adhesive compositions comprising biogenic reactive diluents and resins.
This patent application is currently assigned to Fischerwerke GMBH & Co. KG. The applicant listed for this patent is FISCHERWERKE GMBH & CO. KG. Invention is credited to Jurgen GRUN, Christian SCHLENK, Martin VOGEL, Christian WEINELT.
Application Number | 20160060493 14/779855 |
Document ID | / |
Family ID | 50588618 |
Filed Date | 2016-03-03 |
United States Patent
Application |
20160060493 |
Kind Code |
A1 |
GRUN; Jurgen ; et
al. |
March 3, 2016 |
SYNTHETIC-RESIN ADHESIVE COMPOSITIONS COMPRISING BIOGENIC REACTIVE
DILUENTS AND RESINS
Abstract
Multi-component synthetic resin adhesive composition for the
fixing sector, especially for adhesively bonding an anchoring
element in a hole or crevice, comprising reactive diluents and/or
resins and optionally further additives, characterised in that the
reactive diluent and/or the resin comprise(s) at least one reactive
diluent and/or resin having biogenic content, and the use thereof
in the fixing sector, and related aspects.
Inventors: |
GRUN; Jurgen; (Botzingen,
DE) ; VOGEL; Martin; (Glottertal, DE) ;
SCHLENK; Christian; (Denzlingen, DE) ; WEINELT;
Christian; (Emmendingen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FISCHERWERKE GMBH & CO. KG |
Waldachtal |
|
DE |
|
|
Assignee: |
Fischerwerke GMBH & Co.
KG
Waldachtal
DE
|
Family ID: |
50588618 |
Appl. No.: |
14/779855 |
Filed: |
March 21, 2014 |
PCT Filed: |
March 21, 2014 |
PCT NO: |
PCT/EP2014/000774 |
371 Date: |
September 24, 2015 |
Current U.S.
Class: |
156/307.1 ;
523/437; 524/517; 524/523; 525/206; 525/208; 525/219 |
Current CPC
Class: |
Y02W 30/97 20150501;
C09J 4/00 20130101; C04B 2111/00637 20130101; Y02W 30/91 20150501;
C04B 26/14 20130101; C04B 2111/70 20130101; C04B 2111/00715
20130101; C09J 2433/003 20130101; C08K 3/34 20130101; C09J 133/14
20130101; C08F 222/1067 20200201; C08F 220/281 20200201; C08F
222/1067 20200201; C08F 220/1811 20200201; C08F 222/1067 20200201;
C08F 222/102 20200201; C08F 222/1067 20200201; C08F 220/1818
20200201; C04B 26/14 20130101; C04B 14/06 20130101; C04B 14/066
20130101; C04B 18/248 20130101; C04B 24/2641 20130101; C04B 24/34
20130101; C04B 40/065 20130101; C04B 2103/10 20130101; C04B 2103/20
20130101; C04B 2103/408 20130101; C04B 2103/44 20130101; C04B
2103/54 20130101; C08F 222/1067 20200201; C08F 220/1818
20200201 |
International
Class: |
C09J 133/14 20060101
C09J133/14; C08K 3/34 20060101 C08K003/34 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 5, 2013 |
DE |
10 2013 103 399.7 |
Claims
1. A multi-component synthetic resin adhesive composition for the
fixing, comprising reactive diluents and/or resins, wherein the
reactive diluent and/or the reactive resin comprise(s) at least one
reactive diluent and/or reactive resin that is biogenic or has a
biogenic content.
2. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the reactive diluent or the reactive
resin having biogenic content from those having one or more
reactive groups which are obtainable by reaction of, on the one
hand, one or more starting materials selected from non-biogenic or
biogenic epichlorohydrin and non-biogenic or biogenic (meth)acrylic
acid with OH-- or SH-- or amino (NH.sub.2--) or imino (--NH--)
groups contained in likewise biogenic complementary starting
materials, or two or more of those groups, wherein at least one of
the mentioned starting materials is at least partly biogenic.
3. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the reactive diluents and/or reactive
synthetic resins having biogenic content are (meth)acrylates,
having a biogenic (meth)acrylate portion, of
hydroxy-group-containing vegetable oils, entirely or at least
partly biogenic alkane(mono-, di-, tri-, tetra-, penta-, hexa- or
poly-)ol (meth)acrylates, entirely or partly biogenic
(meth)acrylates of sugar alcohols, entirely or partly biogenic
(meth)acrylated fusel oils, entirely or partly biogenic 5- or
6-membered ring heterocyclyl(meth)acrylates, partly or preferably
entirely biogenic glycerol- or polyglycerol-(meth)acrylates,
entirely or partly biogenic saccharide methacrylates, or UP resins
with biogenic or non-biogenic polycarboxyl compounds and biogenic
or non-biogenic di- or poly-ols, wherein at least one of the
carboxyl and di- or poly-ol radicals is biogenic.
4. The multi-component synthetic resin adhesive composition
according to claim 1, characterised in that the reactive diluents
having biogenic content are epoxidised soybean oil (meth)acrylate,
1,10-decanediol di(meth)acrylate, tetrahydrofuryl methacrylate,
isobornyl methacrylate, sorbitol(meth)acrylate, (meth)acrylated
fusel oil, or purely biogenic glycerol tri(meth)acrylate or one in
which at least the (meth)acrylate portion is biogenic, or mixtures
of two or more such at least partly biogenic reactive diluents.
5. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the reactive diluents having biogenic
content are those selected from entirely or partly, in the glycidyl
portion, biogenic alkane(mono-, di-, tri-, tetra-, penta-, hexa- or
poly-)ol (mono-, di-, tri-, tetra-, penta-, hexa- or poly-)glycidyl
ethers.
6. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the proportion of reactive diluent
having biogenic content is from 0.5% to 80% by weight, based on all
components of the adhesive composition apart from the
packaging.
7. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the proportion of biogenic carbon,
determinable in accordance with the certification program for
bio-based products according to ASTM 6866 by TUV Rheinland, based
on the total formulation without packaging, is at least 20, >50,
at least 55, at least 60, at least 65, at least 75, at least 80 or
>85% by weight.
8. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the synthetic resin adhesive
composition is a two-component kit, having a reactive synthetic
resin component (A) and a hardener component (B).
9. The multi-component synthetic resin adhesive composition
according to claim 8, comprising the content of reactive diluent
having biogenic content in the synthetic resin component (A).
10. The multi-component synthetic resin adhesive composition
according to claim 8, comprising a hardener having biogenic content
in the hardener component (B).
11. The multi-component synthetic resin adhesive composition
according to claim 1, comprising, as a reactive synthetic resin
component (A), a reactive synthetic resin based on epoxy or a
free-radical-hardenable reactive synthetic resin, and also
comprising a hardener component (B).
12. The multi-component synthetic resin adhesive composition
according to claim 11, comprising, as reactive synthetic resin
component (A), a free-radical-hardenable reactive synthetic resin
and, as hardener component (B), such a component having a peroxide
as initiator.
13. The multi-component synthetic resin adhesive composition
according to claim 11, characterised in that it comprises, in the
or a reactive synthetic resin component (A), epoxy(meth)acrylates
of formula ##STR00005## wherein n denotes a number greater than or
equal to 1, and/or propoxylated or ethoxylated aromatic
diol-(meth)acrylates of formula ##STR00006## wherein a and b each
independently of the other denote a number greater than or equal to
0, with the proviso that preferably at least one of the values is
greater than 0, preferably both values being 1 or more, and/or one
or more urethane(meth)acrylates.
14. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the hardenable (=hardening in the
presence of hardener) reactive resin(s) based on epoxy in the
reactive synthetic resin component (A) comprise(s), as epoxy,
polyglycidyl ethers of novolak, bisphenol F or bisphenol A, or
mixtures of such epoxides, preferably entirely or partly of
biogenic nature, and, in the hardener component (B), as hardener,
those having two or more groups selected from amino, imino and
mercapto, for example corresponding amines or thiols, or
furthermore thioalcohols, aminoalcohols or aminothiols, entirely or
partly bio-based Mannich base formulations, or mixtures of such
compounds.
15. The multi-component synthetic resin adhesive composition
according to claim 1, comprising one or more further ingredients,
selected from aminic accelerators, inhibitors (in the case of
free-radical reactive resins), reactive diluents, thixotropic
agents, further fillers and furthermore further ingredients.
16. The multi-component synthetic resin adhesive composition
according to claim 1, wherein the synthetic resin adhesive
composition is a two-component system, in the form of a two-chamber
cartridge with or without a static mixer.
17. A two-component or multi-component synthetic resin adhesive
composition, comprising: a.) a hardenable reactive resin; b.) a
hardenable reactive diluent having a viscosity <800 mPa*s,
measurable using a Brookfield viscometer at 23.degree. C. with a
no. 3 spindle at 20 rpm; c.) a hardener, by means of which a.) and
b.) are hardened and/or by means of which the hardening thereof is
initiated; and wherein the content of biogenic carbon is
>20%.
18. A method of using a multi-component synthetic resin adhesive
composition according to claim 1, comprising introducing the
synthetic resin adhesive composition and an anchoring means into a
hole or crevice, and causing the synthetic resin adhesive
composition to cure.
19. (canceled)
20. A method of producing the multi-component synthetic resin
adhesive composition according to claim 1, comprising introducing
at least one reactive diluent comprising a reactive diluent having
biogenic content.
Description
TECHNICAL FIELD OF THE INVENTION
[0001] The invention relates to multi-component synthetic resin
adhesive compositions for the fixing sector, especially for
adhesively bonding an anchoring element in a hole (for example, a
drilled hole) or crevice, comprising reactive diluents, resins and
optionally further additives, and to further subject-matter of the
invention mentioned hereinbelow.
DISCUSSION OF RELATED ART
[0002] A multiplicity of (for example, injectable) fixing mortar
systems (synthetic resin adhesive compositions) based on an
extremely wide variety of polymer-forming components is known,
sometimes in the form of single-component systems and sometimes in
the form of two-component or multi-component systems, which are
used for embedding anchoring means, such as bolts, anchor rods or
the like, in mortar in holes, such as drilled holes, or crevices,
in each case in solid substrates such as, for example, masonry or
concrete. Further components, for example facing elements, can then
be fixed to the anchoring means. The embedding of the anchoring
means in mortar is based, on the one hand, on adhesive effects in
the sense of a material-bonded connection between the synthetic
resin and an anchoring element and/or the wetted surface of the
hole or crevice and/or, on the other hand, on an interlocking
connection, such as, for example, undercuts formed by using the
synthetic mortar to surround projecting or recessed portions of the
anchoring element and/or of a hole or crevice.
[0003] Documents such as WO 2010130919A1 (glue-like compositions
for wood products, for example with biogenic polyols), WO
2009087360 A1 (binders for chipboards and the like, for example
with glycerol from biodiesel production as additive to silicate
solutions); WO 2011019997 A1, WO 2011020010 A1, and WO 2011020004
A1 (polyols such as castor oil or glycerol as reaction components
in urethane production for shaped bodies with isocyanates); WO
2008/014549 A1 (inter alia polyols as constituents of phenol
resins), or WO 2007112104 A1 (polyols as reaction partners for
isocyanates for forming polyurethane moulded bodies) describe
additives that are partly of vegetable origin.
[0004] Other documents from the prior art, for example EP 1 118 628
A1 or WO 2003044114 A1, relate to mortar compositions as, in the
first case, two-component epoxy-based products as, in the second
case, adhesives for securing nuts to screws based on
free-radical-hardenable resins which comprise glycerol triglycidyl
ethers or alkanediol(meth)acrylates and glycerol(methacrylates) as
components, but they are not characterised as biogenic.
[0005] The prior art accordingly relates to problems and solutions
that differ from the present invention.
[0006] In the synthetic resins and plastics sector there is, for
ecological and economic reasons and as a result of legislation
making it favourable, a requirement to reduce the organically bound
carbon content of fossil constituents (obtained, for example, from
petroleum, lignite coal or bituminous coal).
[0007] Biomass and/or biosphere-based (renewable, sustainable,
bio-based) or just "biogenic" raw materials for carbon are sparing
of resources and, because of their long-term obtainability, are of
special interest.
[0008] In order to assess the proportion of bio-based raw materials
it is customary to ascertain the proportion of bio-based carbon,
which is detected by means of the .sup.14C method. Because the
ratio of carbon isotopes can still be determined after the
production process, it is possible to distinguish between fossil
and biogenic biomass.
[0009] Bio-based products can consist entirely or at least partly
of bio-based raw materials. It is also possible for further
additional substances, inorganic substances or fossil materials, or
two or more thereof, to be included.
[0010] Efforts are being made to make standardised certifications
for products with bio-based contents possible. An example is the
certification program for bio-based products according to ASTM 6866
by TUV Rheinland (DIN CERTCO, Berlin, Germany) in order to gain the
right to mark a product with the certification "Bio-based . . . %,
DIN-tested", for example "Bio-based 50 to 85%, DIN-tested".
[0011] In order to gain such certification, a double minimum
requirement is imposed: firstly, the minimum content of organic
material, determinable as loss on ignition, must be at least 50% by
weight.
[0012] Secondly, the content of bio-based carbon must exceed 20% by
weight (for a certification of "Bio-based 20 to 50%, DIN-tested",
it must be between 20 and 50% by weight; for a certification of
"Bio-based 50 to 85%, DIN-tested", it must be between 50 and 85% by
weight; for a certification of "Bio-based >85%, DIN-tested", it
must be at least 85% by weight).
[0013] Testing of a product is carried out by taking samples from
production or from marketing/selling channels (usually by the
manufacturer or the seller themselves) and testing them. An initial
test is carried out, and regular monitoring.
[0014] In this, the loss on ignition can be determined by customary
methods. It corresponds to the amount of organic material. A known
mass m.sub.0 of test material is ashed, and the mass of the solid
residue obtained m.sub.f is determined and subtracted from m.sub.0.
This corresponds to the volatile and/or organic content of the test
material. A high loss on ignition indicates a high organic
substance content in the sample, because the carbon contained
therein is oxidised and is given off in the form of carbon dioxide.
The determination can be carried out, for example, in accordance
with DIN EN 14775 or DIN 18128.
[0015] The bio-based carbon content is carried out on the basis of
ASTM 6866 (Standard Test Method for Determining the Biobased
Content of Solid, Liquid and Gaseous Samples Using Radiocarbon
Analysis (ASTM International, D6866-12: 2008, Method A).
SUMMARY OF THE INVENTION
[0016] A problem of the invention was to increase the proportion of
biogenic materials in synthetic resin adhesive compositions and in
that way improve environmental and sustainability-related product
indicators (as determined, for example, in a life cycle inventory
analysis in the context of an Environmental Product Declaration
(EPD) or "Carbon Footprint"). The consumption of energy should be
reduced and the carbon dioxide balance improved.
[0017] A further objective is for the fixing systems to have a
bio-based C content of >20, especially >50, >55, >60,
>65, >70, >75 or >80% (tested in accordance with ASTM
6866) (accordingly, preferred variants of the invention are
characterised by such contents).
[0018] It has now been found that (where mentioned, in each case)
biogenic reactive diluents and resins are excellently suitable for
realising synthetic resin adhesive compositions of the kind
mentioned at the outset.
[0019] The invention accordingly relates, in a first embodiment, to
a multi-component synthetic resin adhesive composition as mentioned
at the outset, characterised in that it comprises as reactive
diluent and/or as resin at least one reactive diluent and/or
reactive resin that is biogenic or has a biogenic content,
preferably at least one such reactive diluent and/or resin that is
biogenic or has a biogenic content.
[0020] Corresponding processes and methods for embedding anchoring
elements in mortar and holes or crevices, wherein a multi-component
synthetic resin adhesive composition according to the invention is
used for the embedding of anchoring means in mortar, wherein the
synthetic resin adhesive composition and an anchoring means are
successively, especially first the synthetic resin adhesive
composition and then the anchoring means, or (at least
substantially) simultaneously introduced into a hole or crevice in
a substrate (also in a cracked substrate, such as in cracked
concrete), also form embodiments of the invention.
[0021] The invention also relates, in a further embodiment, to use
of a mentioned reactive biogenic diluent and/or biogenic resin, or
in each case mixtures of two or more thereof, as reactive diluent
and/or resin for multi-component synthetic resin adhesive
compositions, especially for the purposes according to the
invention, wherein preferably the corresponding reactive diluent is
added to a composition of such a kind.
[0022] The definitions hereinbelow serve to clarify certain terms
or symbols and to describe special embodiments of the invention; in
the embodiments of the invention mentioned hereinabove and
hereinbelow it is possible for individual, some or all terms or
symbols to be replaced by more specific definitions, resulting in
special embodiments of the invention.
[0023] Biogenic means preferably that the reactive diluents or
resins or ("having biogenic content") at least parts of their
molecules, and optionally other biogenic components, are obtained
from plants or vegetable materials or furthermore from animal
materials. It is very preferable that the biogenic character can be
detected with reference to ASTM 6866 (by way of the C.sup.14
content), as described above.
[0024] Where weights are given in percent (% by weight), these
relate, if not otherwise stated, to the total mass of the reactants
and additives of the synthetic resin adhesive composition according
to the invention (that is to say to the constituents and/or their
precursors present in the composition to be cured after mixing,
without packaging, except in the case of capsules or films which
can also act as fillers and make a contribution to the total mass
of the hardening or hardened material, and without other possible
parts such as static mixers, cartridge housings or the like).
[0025] Where reference is made to biogenic resins or those having
biogenic content, they are preferably to be understood as including
reactive natural or, especially, synthetic resins of such a
kind.
[0026] Where mention is made of (meth)acrylates, this means
acrylates, methacrylates or mixtures thereof.
[0027] Reactive diluents or resins having biogenic content are
preferably those having one or, preferably, more reactive groups
(groups allowing (co)polymerisation, that is to say especially
unsaturated or epoxy groups), that is to say especially all at
least partly (=in at least one part of the molecule) biogenic
starting materials (raw materials) which are functionalised by
(preferably biogenic) epichlorohydrin or (meth)acrylic acid, for
example by means of OH-- or furthermore SH-- or amino (NH.sub.2--)
or imino (--NH--) groups contained in the (preferably likewise
biogenic) complementary (that is to say reacting with the
epichlorohydrin or (meth)acrylic acid to form the end product)
starting materials (raw materials), or two or more of those groups
(or the reactive diluents and resins obtainable by reaction of
those starting materials), especially those which contain hydroxyl
groups and thus are functionalised to form (correspondingly
entirely or at least partly biogenic) (meth)acrylic acid esters or
glycidyl ethers, or furthermore those having a correspondingly
functionalised amino or carboxyl (COOH) group, such as, for
example, (meth)acrylates (preferably having a biogenic
(meth)acrylate portion) of hydroxy-group-containing vegetable oils,
such as of castor oil or soybean oil, entirely or at least partly
biogenic (for example C.sub.1-C.sub.10)alkane(mono-, di-, tri-,
tetra-, penta- or hexa- or poly-)ol (meth)acrylates, partly or
preferably entirely biogenic polyglycerol(meth)acrylates, entirely
or partly biogenic (meth)acrylates of sugar alcohols, such as
mannitol, xylitol or sorbitol, entirely or partly biogenic
(meth)acrylated fusel oils, entirely or partly biogenic 5- or
6-membered ring heterocyclyl(meth)acrylates (especially having one
or two hetero atoms selected from O, N and S in the ring), partly
or preferably entirely biogenic glycerol- or
polyglycerol-(meth)acrylates, entirely or partly biogenic
saccharide methacrylates, or UP resins with biogenic or
non-biogenic polycarboxyl compounds and biogenic or non-biogenic
di- or poly-ols or mixed-functional compounds such as, for example,
biogenic lactic acid, wherein at least one of the carboxyl and di-
or poly-ol radicals is biogenic; or partly or entirely biogenic
C.sub.2-C.sub.12 alkyl((mono-, di-, tri-, tetra-, penta-, hexa- or
poly-)ol (mono-, di-, tri-, tetra-, penta-, hexa- or poly-)glycidyl
ethers), such as trimethylolpropane triglycidyl ether or glycerol
triglycidyl ether.
[0028] Preferably (especially in the case of products according to
the invention) the reactive diluent having biogenic content is not
epoxidised castor oil.
[0029] Special preference is given to epoxidised soybean oil
(meth)acrylate, 1,10-decanediol di(meth)acrylate, tetrahydrofuryl
methacrylate, isobornyl(meth)acrylate, sorbitol(meth)acrylate,
(meth)acrylated fusel oil, or purely biogenic glycerol
tri(meth)acrylate or one in which at least the (meth)acrylate
portion is biogenic, or in the case of epoxides entirely or partly
(especially in the glycidyl portion) biogenic alkane(mono-, di-,
tri-, tetra-, penta-, hexa- or poly-)ol (mono-, di-, tri-, tetra-,
penta-, hexa- or poly-)glycidyl ethers, such as trimethylolpropane
triglycidyl ether, or partly or preferably entirely biogenic
glycerol triglycidyl ether, partly biogenic epoxy resin based on
phenols, such as novolak, bisphenol F or bisphenol A or suitable
(suitable for the unsaturated or epoxy-based system in question)
mixtures of two or more such at least partly biogenic reactive
diluents or at least partly biogenic reactive resins are possible.
As the person skilled in the art knows, technically often only
partly functionalised species are obtained (that is to say, for
example, those which have, for example, 3 hydroxy groups per
molecule and accordingly can in theory be tri-functionalised, but
in practice are functionalised only to a lesser degree, for example
on average 2.7-fold), which are also to be covered herein in each
case without further reference.
[0030] In special cases the (meth)acrylic acid or epichlorohydrin
portion is also of biogenic origin. In particular epichlorohydrin
(Bruce M. Bell et al: Glycerin as a Renewable Feedstock for
Epichlorohydrin Production. The GTE Process. Clean 36 (8), 2008;
pages 657-661) and (meth)acrylic acid (for example in accordance
with EP 1 710 227 B1, DE 10 2008 038 273 A1 or "Einfuhrung in die
Technische Chemie" [Introduction to Technical Chemistry], Arno
Behr, David W. Agar, Jakob Jorissen, Spektrum Akademischer Verlag
Heidelberg, 2010, page 139) can be produced in accordance with
methods known per se from glycerol and lactic acid,
respectively.
[0031] The reactive diluents having biogenic content are added, for
example, in a proportion of from 0.5 to 80% by weight, for example
from 1 to 55% by weight. One example of suitable proportions is in
the range from 1 to 35% by weight; another example is in the range
from 36 to 60% by weight.
[0032] "Comprise" or "include" means that other components or
features may be present in addition to the components or features
mentioned and therefore does not refer to an exhaustive list,
unlike "contain", the use of which does signify an exhaustive list
of components or features.
[0033] Where the attribute "furthermore" is mentioned, this means
that features without this attribute can be more preferred.
[0034] "And/or" means that the mentioned features/substances can in
each case be present on their own or in a combination of two or
more of the individually mentioned features/substances.
[0035] "A" usually denotes the indefinite article (except when it
is recognisable as a number as immediately afterwards in this
sentence) and especially means "at least one" (in the sense of 1, 2
or more).
[0036] As the synthetic resin there are used primarily reactive
synthetic resins based on epoxy or free-radical-hardenable
(=hardening after addition of a free-radical-former (hardener))
reactive synthetic resins (hardenable component), which in each
case can be hardened by appropriate hardeners (hardener
components), as described, for example, hereinbelow.
[0037] Synthetic Resins Based on Epoxy:
[0038] The reactive synthetic resins based on epoxy that can be
utilised in use of and/or in multi-component synthetic resin
adhesive compositions according to the invention comprise an epoxy
component, preferably based on glycidyl compounds, for example
those having an average glycidyl group functionality of 1.5 or
more, especially of 2 or more, for example from 2 to 10, which can
optionally comprise further glycidyl ether(s) as reactive diluent.
The epoxides of the epoxy component are preferably poly(including
di)-glycidyl ethers of at least one polyhydric alcohol or phenol,
such as novolak, bisphenol F or bisphenol A, or mixtures of such
epoxides, for example obtainable by reaction of the corresponding
polyhydric alcohols with epichlorohydrin. Examples are
trimethylolpropane triglycidyl ether, novolak epoxy resins,
bisphenol A epichlorohydrin resins and/or bisphenol F
epichlorohydrin resins, for example having an average molecular
weight of .ltoreq.2000 Da. The epoxy resins can have, for example,
an epoxy equivalent of from 120 to 2000, preferably from 150 to
400, such as especially from 155 to 195, for example from 165 to
185. In a variant according to the invention, resins that have been
produced at least partly from biogenic constituents are preferred,
because they increase the proportion of biogenic carbon, such as,
for example, bisphenol-A-, bisphenol-F- or bisphenol-NF-resins
having a biogenic glycidyl portion (obtainable, for example, from
Spolchemie, Revolu{hacek over (c)}ni 1930/86, 400 32 sti nad Labem,
Czech Republic). The proportion in the total mass of the reactants
and additives of the injectable synthetic mortar system is
preferably from 5 to below 100% by weight, especially from 10 to
80% by weight, from 10 to 70% by weight or from 10 to 60% by
weight. Also possible are mixtures of two or more such epoxy
components. Suitable epoxy resins, reactive diluents and hardeners
are also to be found in the reference work by Lee H and Neville K,
"Handbook of Epoxy Resins" (New York: McGraw-Hill), 1982 (these
compounds are incorporated herein by reference).
[0039] "Based on epoxy" means especially that the synthetic resin
adhesive compositions according to the invention can also comprise,
in addition to the components mentioned hitherto, further customary
ingredients (for example, additives or other constituents mentioned
hereinabove or hereinbelow). These further ingredients can be
present, for example, in an amount of, in total, up to 80% by
weight, preferably between 0.01 and 65% by weight. Even when "based
on" is not explicitly mentioned, such customary ingredients are
also included.
[0040] Important examples of further ingredients are one or more
selected from accelerators, non-reactive diluents or further
(besides the biogenic) reactive diluents, thixotropic agents,
fillers and further additives.
[0041] As accelerators there may be included, for example,
tert-amines, such as imidazoles or tert-aminophenols, such as
2,4,6-trimethylaminomethylphenol, organophosphines or Lewis bases
or Lewis acids, such as phosphoric acid esters, or mixtures of two
or more thereof, in one or (especially in the case of
multi-component systems) more of the components, preferably in each
case in a hardener component, for example in a proportion by weight
of from 0.001 to 15% by weight, based on the total mass of the
reactants and additives of the injectable synthetic mortar
system.
[0042] As thixotropic agents there can be used customary rheology
aids, such as pyrogenic silica (especially, for example,
surface-treated to be made hydrophobic) or hydrogenated (solid at
room temperature) or hydroxyalkylated castor oils. They can be
added, for example, in a proportion by weight of from 0.001 to 50%
by weight, for example from 0.5 to 20% by weight.
[0043] The fillers can be present in one or more components, for
example of a multi-component kit according to the invention, for
example in one or both components of a corresponding two-component
kit; the proportion of further fillers is preferably from 0 to 90%
by weight, for example from 10 to 90% by weight. Biogenic fillers,
such as lignin sulfonates, kernel flours or shell flours from
fruits, for example coconut shell flour, walnut shell flour or
olive stone flour, or vegetable charcoal, or mixtures of two or
more thereof, can be used for this purpose. Non-biogenic fillers,
such as corundum, quartz sand or quartz powder, can also be added.
Furthermore, hydraulically hardenable fillers, such as gypsum,
burnt lime or cement (for example, alumina cement or Portland
cement), water glasses or active aluminium hydroxides, or two or
more thereof, can be added.
[0044] Further ingredients can also be added, such as plasticisers,
non-reactive diluting agents, flexibilisers, stabilisers, rheology
aids, wetting and dispersing agents, colouring additives, such as
dyes or especially pigments, for example for staining the
components different colours for better monitoring of their
intermixing, or the like, mixtures of two or more thereof. Such
further additives can preferably be added in total in proportions
by weight of in total from 0 to 90%, for example from 0 to 40% by
weight.
[0045] Some of the compounds mentioned in the definition of
epoxides, such as trimethylolpropane triglycidyl ether or
hexanediol diglycidyl ether or glycidyloxypropyl-trimethoxysilane,
which have a lower viscosity than epoxides comprising aromatic
groups, can also be used as further reactive diluents, for example
in a proportion by weight of from 0.1 to 90% by weight, for example
between 0.5 and 75% by weight or between 1 and 40% by weight.
[0046] The hardener comprises at least one compound customary for
epoxy hardening (reaction partner in polyaddition), the term
"hardener" meaning preferably at least one compound which is
customary for epoxy hardening with or without addition of fillers
(especially biogenic fillers according to the invention) and/or
further additives, such as water, thickeners and/or further
additional substances, such as dyes and the like, in other words
the complete hardener component. The hardener can be in the form of
a separate component and/or also be incorporated (especially in
protected form, that is to say, for example, in micro-encapsulated
form) in the reactive resin formulation (in the form of a
hardenable component, that is to say one which, after mixing with
the hardener after breaking-open of the casing of the microcapsule,
cures by means of polymerisation). Customary additives can be
added, such as, for example, fillers (especially as defined
hereinabove) and/or solvents (non-reactive diluents) (especially
for producing a paste or emulsion), such as benzyl alcohol and/or
water.
[0047] The compounds customary for epoxy hardening (which function
as reaction partners in the course of polyaddition) are especially
those having two or more groups selected from amino, imino and
mercapto, for example corresponding amines (preferred), thiols or
aminothiols, or mixtures of two or more thereof, for example as
mentioned in Lee H and Neville K, "Handbook of Epoxy Resins" (New
York: McGraw-Hill), 1982, which is incorporated herein by reference
in this regard, for example di- or poly-amines mentioned therein,
and/or di- or poly-thiols.
[0048] In special embodiments of the invention, the compounds
customary for epoxy hardening, the epoxy base or both have no
rubber modification.
[0049] The compounds customary (generally) for epoxy hardening
include, for example in an embodiment of the invention [0050] di-
or poly-amines such as especially aliphatic (such as
ethylenediamine), cyclo-aliphatic and aromatic di- or poly-amines,
amidoamines, amine adducts, polyether diamines or
polyphenyl/polymethylenepolyamines, Mannich bases, polyamides and
the like (special mention being made of Mannich bases, especially
as disclosed in the publication WO 2005/090433, especially on page
3, final paragraph, to page 6, second paragraph, as in Example 1
or, especially, 2 thereof, which is incorporated herein by
reference in this regard, or very especially based on (biogenic)
cardanol, on their own or in admixture with one or more further di-
or poly-amines); [0051] di- or poly-thiols such as especially
di-functional or higher functional thiols, for example
dimercapto-.alpha.,.omega.-C1-C12alkanes,
4,4'-dimercaptodicyclohexylmethane, di-mercaptodiphenylmethane or
the like; [0052] furthermore aliphatic aminols, such as especially
hydroxy-lower alkylamines, such as ethanolamine, diethanolamine or
3-aminopropanol, or aromatic aminols, such as 2-, 3- or
4-aminophenol.
[0053] Mixtures of two or more of the mentioned compounds customary
for epoxy hardening can also be used and/or included.
[0054] The compounds customary for epoxy hardening, where present,
are present preferably in amounts of up to 95% by weight,
preferably from 2 to 70% by weight, based on the total mass of
reactants and additives in the mass of the synthetic resin adhesive
composition to be cured (for example, the injectable synthetic
resin system).
[0055] Based on the hardener component of a multi-component
synthetic resin adhesive composition according to the invention,
the proportion of the corresponding compounds in a possible
preferred embodiment of the invention is from 1 to 100% by weight,
for example 4 to 95% by weight, 5 to 90% by weight or 10 to 80% by
weight.
[0056] Especially in the case of a hardener component of a
multi-component system according to the invention, further
additives can also be constituents of the "hardener", such as
water, organic solvents, such as benzyl alcohol, fillers (for
example as mentioned hereinabove) and further ingredients from the
ingredients mentioned hereinabove, for example in a proportion by
weight of, in total, from 0.01 to 70% by weight, for example from 1
to 40% by weight.
[0057] Free-Radical-Hardenable Reactive Synthetic Resins
[0058] The free-radical-hardenable reactive synthetic resins
(preferred in embodiments of the invention) are primarily those
based on free-radical-hardening unsaturated reactive resins and,
present in a separate component, free-radical hardeners.
[0059] Preferably, no input of heat and/or (for example, UV) light
from the outside is necessary for their use.
[0060] Free-radical-hardening unsaturated reactive resins are to be
understood as being primarily those which comprise, as
free-radical-curing (which includes "curable (for example prior to
addition of hardener)") components, organic compounds having
unsaturated (for example olefinic) radicals or, especially, which
consist of such compounds, especially those which comprise 2 or
more unsaturated (olefinic) radicals per molecule, primarily those
which include hardenable esters with unsaturated carboxylic acid
radicals; preferably in each case propoxylated or, especially,
ethoxylated aromatic diol-, such as bisphenol-A-, bisphenol-F- or
novolak-(especially di-)(meth)acrylate, epoxy(meth)acrylates,
especially in the form especially of reaction products of di- or
poly-epoxides, for example bisphenol-A-, bisphenol-F- or
novolak-di- and/or -poly-glycidyl ethers, with unsaturated
carboxylic acids, for example C.sub.2-C.sub.7alkenecarboxylic
acids, such as especially (meth)acrylic acid, urethane- and/or
urea-(meth)acrylates (which also includes oligomeric or polymeric
variants), and/or unsaturated polyester resins, or the like; for
example having an average molecular weight of .ltoreq.2000; or two
or more of such hardenable unsaturated organic components; for
example they are present in a proportion by weight of from 0.1 to
90% by weight, for example between 0.5 and 75% by weight or between
1 and 40% by weight or from 40 to 65% by weight.
[0061] Examples of epoxy(meth)acrylates present in and/or used in
special embodiments of the invention are those of formula
##STR00001##
or, more generally, taking into account the prelengthening reaction
in the preparation of the bisphenol A diglycidyl ether of
formula
##STR00002##
wherein n denotes a number greater than or equal to 1 (when
mixtures of different molecules having different n values are
present and are represented by the formula, non-integer numbers are
also possible as a mean value). These too are subsumed hereinbelow
under the term "vinyl esters".
[0062] Examples of propoxylated or, especially, ethoxylated
aromatic diol-, such as bisphenol-A-, bisphenol-F- or
novolak-(especially di-)(meth)acrylates present in and/or used in
special embodiments of the invention are those of formula
##STR00003##
or, generally, also taking into account higher degrees of
ethoxylation:
##STR00004##
wherein a and b each independently of the other denote a number
greater than or equal to 0, with the proviso that preferably at
least one of the values is greater than 0, preferably both values
being 1 or more (when mixtures of different molecules having
different (a and b) values are present and are represented by the
formula, non-integer numbers are also possible as a mean value, but
for individual molecules seen in isolation only integers in each
case). These too are subsumed hereinbelow under the term "vinyl
esters".
[0063] Important examples of further ingredients here are aminic
accelerators, inhibitors, non-reactive diluents or further (besides
the biogenic) reactive diluents, thixotropic agents, fillers and/or
further additives.
[0064] As aminic accelerators there come into consideration those
having sufficiently great activity, such as especially (preferably
tertiary, especially hydroxyalkylamino-group-substituted) aromatic
amines selected from the group selected from epoxyalkylated
anilines, toluidines or xylidines, such as, for example,
ethoxylated toluidine, aniline or xylidine, for example
N,N-bis(hydroxypropyl or hydroxyethyl)-toluidines or -xylidines,
such as N,N-bis(hydroxypropyl or hydroxyethyl)-p-toluidine,
N,N-bis(hydroxyethyl)-xylidine and more especially corresponding
higher alkoxylated technical products. One or more such
accelerators are possible. The accelerators preferably have a
content (concentration) of from 0.005 to 10%, especially from 0.1
to 5% by weight.
[0065] As inhibitors there can be added, for example, non-phenolic
(anaerobic) and/or phenolic inhibitors.
[0066] As phenolic inhibitors (which are often provided as a
component already mixed in with commercial free-radical-hardening
reactive resins but which, furthermore, may also be absent) there
come into consideration (non-alkylated or alkylated) hydroquinones,
such as hydroquinone, mono-, di- or tri-methyl hydroquinone,
(non-alkylated or alkylated) phenols, such as
4,4'-methylene-bis(2,6-di-tert-butylphenol),
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene,
(non-alkylated or alkylated) pyro-catechols such as
tert-butyl-pyrocatechol, 3,5-di-tert-butyl-1,2-benzenediol, or
especially 4-methoxyphenol, or mixtures of two or more thereof.
These have preferably a content of up to 1% by weight, especially
between 0.0001 and 0.5% by weight, for example between 0.01 and
0.1% by weight.
[0067] As non-phenolic or anaerobic (that is to say, unlike the
phenolic inhibitors, active also without oxygen) inhibitors (which
especially have scarcely any effect on the curing times) there come
into consideration preferably phenothiazine or organic nitroxyl
free radicals. As organic nitroxyl free radicals there can be
added, for example, those described in DE 199 56 509, which are
incorporated herein by reference especially in respect of the
compounds mentioned therein, especially
1-oxyl-2,2,6,6-tetramethyl-piperidin-4-ol ("4-OH-TEMPO" or
"TEMPOL"). The proportion by weight of the non-phenolic inhibitors
is preferably in the range of from 1 ppm (by weight) to 2% by
weight, especially, for example, in the range of from 10 ppm to 1%
by weight, based on the reactive resin formulation.
[0068] As thixotropic agents there can be used customary
thixotropy-imparting rheology aids, such as pyrogenic silica and/or
hydrogenated (solid at room temperature) or hydroxyalkylated castor
oils. They can be added, for example, in a proportion by weight of
from 0.01 to 50% by weight, for example from 0.5 to 20% by
weight.
[0069] As fillers there can be used customary fillers, especially
cements (for example Portland cements or alumina cements), chalks,
sand, quartz sand, quartz powder or the like, which can be added in
the form of powder, in granular form or in the form of shaped
bodies, or other fillers, such as especially kernel flours or shell
flours from plants, which further increases the biogenic carbon
content, such as olive stone flour, coconut shell flour or
furthermore walnut shell flour, or hydraulic fillers, as described
above under the epoxides, or mixtures of two or more thereof, it
being possible for the fillers furthermore or especially also to be
silanised.
[0070] The fillers can be present in one or more components of a
multi-component synthetic resin adhesive composition according to
the invention, for example one or both components of a
corresponding two-component kit; the content of fillers is
preferably from 0 to 90% by weight, for example from 10 to 50% by
weight (in the case of the installation of anchoring elements,
broken casing material (for example splintered glass or splintered
plastics), for example fragments of capsules, can also be counted
as filler). In addition or as an alternative to one or more of the
mentioned fillers, hydraulically hardenable fillers, such as
gypsum, burnt lime or cement (for example alumina cement or
Portland cement), water glasses or active aluminium hydroxides, or
two or more thereof, can be added.
[0071] Further ingredients can also be added, such as plasticisers,
non-reactive diluents, flexibilisers, stabilisers, rheology aids,
wetting and dispersing agents, colouring additives, such as dyes or
especially pigments, for example for staining the components
different colours for better monitoring of their intermixing, or
the like, or other additives, mixtures of two or more thereof. Such
further additives can preferably be added in total in proportions
by weight of in total from 0 to 90%, for example from 0 to 40% by
weight.
[0072] As "further reactive diluents" (in addition to those
according to the invention), for example for preferred vinyl esters
or urethane(meth)acrylates, it is possible, in addition, for one or
more (relatively low-viscosity) free-radical-hardening unsaturated
reactive diluents in non-biogenic form also to be added, which are
to be understood as being primarily those which comprise, as
free-radical-curing (which includes "curable (for example prior to
addition of hardener)") components, organic compounds having
unsaturated (for example, olefinic) radicals or, especially, which
consist of such compounds, for example especially (meth)acrylate or
(meth)acrylamide monomers, such as acrylic acid and/or methacrylic
acid or preferably esters thereof (referred to as (meth)acrylates)
or amides, especially (meth)acrylates such as mono-, di-, tri- or
poly-(meth)acrylates (including hydroxyalkyl(meth)acrylates, such
as hydroxypropyl(meth)acrylate or hydroxyethyl(meth)acrylate,
alkyl(meth)acrylates having 1 to 10 (meth)acrylate groups, such as
mono-, di-, tri-, tetra-, penta-, hexa- or poly-(meth)-acrylates,
for example alkyl di- or tri-(meth)acrylates, such as
1,2-ethanediol di(meth)-acrylate (ethylene glycol
di(meth)acrylate), butanediol di(meth)acrylate, such as 1,3- or
especially 1,4-butanediol di(meth)acrylate, hexanediol
di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylglycol
di(meth)acrylate, trimethylolpropane tri(meth)-acrylate, glycerol
tri(meth)acrylate, polyglycerol poly(meth)acrylate, polyethylene
glycol di(meth)acrylate, cycloalkyl(meth)acrylates,
bicycloalkyl(meth)acrylates or heterocyclyl(meth)acrylates, wherein
cycloalkyl or bicycloalkyl has from 5 to 7 ring carbon atoms and
heterocyclyl has 5 or 6 ring atoms and 1 or 2 ring hetero atoms
selected from N, O and S, such as tetrahydrofurfuryl(meth)acrylate
or isobornyl(meth)acrylate, or acetacetoxyalkyl(meth)acrylate; or
furthermore styrenes, such as styrene, .alpha.-methyl styrene,
vinyl toluene, tert-butyl styrene and/or divinyl benzene; or
mixtures of two or more thereof, as constituents that cure in
parallel with the free-radical-hardening unsaturated reactive
resin, for example in a proportion by weight of from 0.1 to 90% by
weight, for example between 0.5 and 75% by weight or between 1 and
40% by weight.
[0073] As non-reactive diluents there can be added, for example,
vegetable oils, such as castor oil, or furthermore bio-alcohols and
fatty acids and esters thereof, or mixtures of two or more thereof,
for example in a proportion of from 3 to 60% by weight, for example
from 4 to 55% by weight.
[0074] The hardener includes at least one peroxide as actual
initiator. The term "hardener" here preferably hereinabove and
hereinbelow means pure initiators or stabilised initiators, with or
without addition of filler, and/or further additives, such as
water, thickeners and/or further additional substances, such as
dyes, pigments, additives and the like, in other words the complete
hardener component. For stabilisation, customary additives, such as
gypsum, chalk, pyrogenic (preferably surface-treated, such as
hydrophobised) silica, phthalates, chlorinated paraffin or the
like, can be added. In addition, fillers and/or (especially for the
preparation of a paste or emulsion) solvents (non-reactive
diluents, such as, for example, liquid (for example, epoxidised or
hydroxyl-group-containing) oils, for example castor oil, or water,
thickeners, fillers (such as, for example, those mentioned above)
and further additives of those mentioned above can also be added.
The content of all additives can be, for example, a proportion by
weight of in total from 0.1 to 99.5% by weight, for example from 1
to 99.5% by weight.
[0075] Based on the hardener component, the content of initiator
(actual hardener) in a possible preferred embodiment of the
invention is from 0.5 to 90% by weight, especially from 0.9 to 30%
by weight.
[0076] As initiator for the hardening of the reactive resin
formulations according to the invention there are used in the case
of free-radical polymerisation, for example free-radical-forming
peroxides, for example organic peroxides, such as diacyl peroxides,
for example dibenzoyl peroxide, ketone peroxides, such as methyl
ethyl ketone peroxide or cyclohexanone peroxide, or alkyl
peresters, such as tert-butyl perbenzoate, inorganic peroxides,
such as persulfates or perborates, and also mixtures thereof.
[0077] The proportion of hardener in a synthetic resin adhesive
composition according to the invention, based on the mass (weight)
of all reactants and additives without packaging, preferably lies
in a range of from 1 to 60% by weight, for example from 2 to 50% by
weight, it being possible for the proportion of peroxide, likewise
based on the mass of the total associated reactive resin
formulation (100%), to be 0.1 or more % by weight, in an especially
preferred embodiment from 0.1 to <1% by weight, furthermore also
from 1 to 10% by weight.
[0078] The free-radical-hardenable unsaturated reactive resin
(and/or the totality of its components) is provided, for example,
in a proportion by weight of from 5 to 99.5%, such as for instance
from 10 to 98.5%, for example from 10 to 89.5%.
[0079] Here too, "based on" means that the synthetic resin adhesive
compositions according to the invention can also include, in
addition to the mentioned components, further customary ingredients
(for example additives or other constituents as mentioned
hereinabove or hereinbelow). Such further ingredients can be
present together, for example in an amount of in total up to 80% by
weight, preferably between 0.01 and 65% by weight. Even where
"based on" is not expressly mentioned, such customary ingredients
are included.
[0080] A hole or crevice is to be understood as being a hole or
crevice that is present in a solid substrate (especially already
completed as such), especially masonry or concrete, optionally also
in a cracked substrate, such as cracked concrete, and is accessible
from at least one side, for example a drilled hole, or furthermore
a recessed region made during mortaring with inorganic mortar or
plastering materials (such as cement or gypsum), or the like.
[0081] In a special embodiment of the subject-matter of the
invention, the hardenable components and the associated hardeners
(hardener components) are stored separately from one another in a
two-component or multi-component system before they are mixed with
one another at the desired site (for example close to or in a hole
or crevice, such as a drilled hole).
[0082] The injectable synthetic resin systems according to the
invention are provided as multi-component systems (for example, a
multi-component kit) and are also used as such.
[0083] A multi-component kit is understood to be especially a
two-component or (furthermore) multi-component kit (preferably a
two-component kit) having a component (A), which comprises either
one or more free-radical-hardenable (=hardening after addition of a
free-radical-former (hardener)) reactive synthetic resins or one or
more reactive synthetic resins based on epoxy, as described
hereinabove and hereinbelow, and the respective associated hardener
(component (B)), as defined hereinabove and hereinbelow, it being
possible for further additives to be provided in one or both of the
components, preferably a two-chamber or furthermore multi-chamber
apparatus, wherein the components (A) and (B) that are able to
react with one another and optionally further separate components
are present in such a way that their constituents cannot react with
one another (especially not curing) during storage, preferably in
such a way that their constituents do not come into contact with
one another prior to use, but that enables components (A) and (B)
and optionally further components to be mixed together for fixing
at the desired location, for example directly in front of or in a
hole, and, if necessary, introduced in such a way that the
hardening reaction can take place therein. Also suitable are
capsules, for example made of plastics, ceramics or especially
glass, in which the components are arranged separated from one
another by means of rupturable boundary walls (which can be
ruptured, for example, when an anchoring element is driven into a
hole or crevice, such as a drilled hole) or integrated separate
rupturable containers, for example in the form of capsules, such as
ampoules, arranged one inside the other; and also especially
multi-component or especially two-component cartridges (which are
likewise especially preferred), the chambers of which contain the
plurality of components or preferably the two components
(especially (A) and (B)) of the synthetic resin adhesive
composition according to the invention having the compositions
mentioned hereinabove and hereinbelow for storage prior to use, the
kit in question preferably also including a static mixer.
[0084] Advantageously, the packaging materials (such as films,
cartridges (also static mixers) or plastics capsules) can likewise
be made from plastics having a high or completely biogenic carbon
content, for example from corresponding polyamides or the like.
[0085] The use of a synthetic resin adhesive composition according
to the invention at the desired site of use is effected by mixing
the associated components (separated before mixing so as to inhibit
a reaction), especially close to and/or directly in front of a hole
or (for example especially when cartridges having static mixers are
used) directly in front of and/or (especially when suitable
capsules or ampoules are broken) inside a hole or crevice, for
example a drilled hole.
[0086] "Embedding in mortar" is especially to be understood as
meaning (material-bonded and/or interlocking) fixing of anchoring
means made of metal (for example undercut anchors, threaded rods,
screws, drill anchors, bolts) or, furthermore, made of some other
material, such as plastics or wood, in solid substrates (preferably
already completed as such), such as concrete or masonry, especially
insofar as they are components of artificially erected structures,
more especially masonry, ceilings, walls, floors, panels, pillars
or the like (for example made of concrete, natural stone, masonry
made of solid blocks or perforated blocks, furthermore plastics or
wood), especially in holes, such as drilled holes. Those anchoring
means can then be used to secure, for example, railings, covering
elements, such as panels, facade elements or other structural
elements.
[0087] Where "mixtures of two or more thereof" are mentioned, this
includes especially mixtures of at least one of the mentioned
constituents, which are emphasised as being preferred, with one or
more other components, especially one or more components likewise
identified as being preferred.
[0088] "Completed as such" means especially that the substrates
are, except for possible surface modifications (such as coating,
for example plastering or painting) or the like, already completed
(for example, as building modules or walls) and are not completed
only at the same time as the adhesive composition or are not made
from the latter. In other words: the adhesive composition itself is
not, then, already-completed substrate.
[0089] The introduction of the anchoring means is preferably
effected only a short time, preferably 30 minutes or less, after
the components of the fixing mortar according to the invention have
been mixed together. In explanation: the mixing/introduction of the
components at/into the desired locations at which anchoring means
are to be fixed initiates a plurality of reactions which proceed
substantially in parallel and/or with only a very small time
interval between them. The final curing takes place in situ.
[0090] Specific embodiments of the invention also relate to the
variants mentioned in the claims and abstract--the claims and the
abstract are therefore incorporated herein by reference.
[0091] The Examples that follow serve to illustrate the invention,
without limiting its scope, but also show special embodiments of
the invention (it also being possible for each individual
specifically mentioned constituent to be used in any of the
subject-matter of the invention mentioned hereinabove and
hereinbelow instead of a general term, or a plurality or all
thereof, which defines special embodiments of the invention).
EXAMPLE 1
Two-Component Adhesive Compositions According to the Invention
Based on Free-Radical-Hardenable Reactive Resins
[0092] Components (A) suitable for use according to the invention
were prepared from the following polymerisable components:
TABLE-US-00001 Mortar 1 Mortar 2 Mortar 3 Mortar 4 Mortar 5 Mortar
6 Content % Content % Content % Content % Content % Content % Raw
material by weight by weight by weight by weight by weight by
weight ethoxylated 19 16 16 17 17 20 bisphenol A dimethacrylate (*)
tetrahydrofurfuryl 9.9 9.9 methacrylate Sarbio 6100* isobornyl 18
methacrylate* epoxidised 5 soybean oil acrylate CN111*
1,10-decanediol 9.9 dimethacrylate Sarbio 5201* polyglycerol 5
acrylate* sorbitol acrylate 5 (BASF)* glycerol 5 trimethacrylate*
methacrylated 9.9 fusel oil* inhibitor mixture 0.05 0.05 0.05 0.05
0.05 0.05 (selected from t-BBC, hydro- quinone and/or tempol)
aminic 0.65 0.65 0.65 0.65 0.65 0.65 accelerator pyrogenic 1.5 1.5
1.5 1.5 1.5 1.5 surface-treated silica quartz powder 41.9 41.9 41.9
43.8 43.9 39.8 olive stone flour 27 25 25 coconut shell 27 25 20
flour 100 100 100 100 100 100 Biocontent [%] 50.5 56 54 54 52 52 *=
reactive diluents or resins according to the invention that are
biogenic or at least have a biogenic content (*) reactive resins
according to the invention that are potentially biogenic or at
least have a biogenic content "Sarbio" is a mark of Sartomer
Europe, Colombes Cedex, France Soybean oil acrylate CN111 is
likewise by Sartomer Europe
[0093] In each case there is used as hardener component (B):
TABLE-US-00002 Hardener component 1 Raw material Amount used [%]
castor oil 40.00 dibenzoyl peroxide 33% 16.00 in inert filler
quartz sand 41.50 pyrogenic surface- 2.00 treated silica pigment
0.50 100.00
[0094] The hardener has a density of 1.50 g/ccm and a viscosity of
120 Pa*s at 23.degree. C., measured using a Brookfield no. 7
spindle at 10 rpm. The bio-carbon content is 88.9%.
[0095] Fixing mortars are prepared with all mortar/hardener
combinations (ratio by volume of component (A) to (B)=5:1). Good to
very good bond strengths in the range of 15-23 N/mm.sup.2 were
achieved with all fixing mortars.
EXAMPLE 2
Two-Component Adhesive Compositions According to the Invention
Based on Epoxy-Based Reactive Resins
[0096] Components (A) suitable for use according to the invention
were prepared from the following polymerisable components:
TABLE-US-00003 Mortar 7 Mortar 8 Mortar 9 Mortar 10 Content Content
Content Content % by % by % by % by Raw material weight weight
weight weight bisphenol A/F resin with 45 45 45 45 a bio-C content
of 28% (Spolchemie) trimethylolpropane 15 5 triglycidyl ether,
bio-C content 64% glycerol triglycidyl ether, 20 20 15 bio-C
content 100% wetting and dispersing 2 2.5 2.5 2 agent pyrogenic
surface-treated 2 2 2 3 silica quartz sand 7.5 lignin sulfonate
10.5 olive stone flour 28 20 coconut shell flour 30 walnut shell
flour 30 pigment 0.5 0.5 100 100 100 100 Biocontent [%] 50 58 56
57
[0097] In each case there is used as hardener component (B):
TABLE-US-00004 Hardener component 1 Raw material Amount used [%]
Mannich base formulation 60.00 based on cardanol vegetable charcoal
37.50 pyrogenic surface-treated 2.50 silica 100.00
[0098] The hardener has a density of 1.28 g/ccm and a viscosity of
160 Pa*s at 23.degree. C., measured using a Brookfield no. 7
spindle at 10 rpm. The bio-carbon content is 73%.
[0099] Fixing mortars are prepared with all mortar/hardener
combinations (ratio by volume of component (A) to (B)=3:1). Very
good bond strengths in the range of 18-25 N/mm.sup.2 were achieved
with the fixing mortars.
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